Decoupling competitive reactions by their differential orbital-coupling response to vacancy engineering for efficient electrocatalytic nitrogen reduction

doi:10.1016/S1872-2067(26)65043-7

Abstract

Abstract:

The electrocatalytic nitrogen reduction reaction (NRR) poses formidable challenges, such as competing hydrogen evolution and poor N₂ activation. Herein, we introduce a precise electronic-structure tuning modality through controlled sulfur vacancy (V_S) engineering in 1T-MoS₂. By manipulating the V_S concentration to nearly 9.38%, the optimized catalyst (MoS₂-100) achieves an outstanding NH₃ yield of 64.50 μg h^-1 mg^-1 and a Faradaic efficiency of 15.25%, superior to most electrocatalysts reported. Mechanistic studies reveal that enhanced d-σ orbital coupling between Mo and N₂ significantly promotes N₂ activation, while the distinct orbital-coupling responses of Mo-N₂ and Mo-H to V_S concentration render a potential competition-preponderance window for NRR. This work establishes a novel paradigm for decoupling the competitive reactions by utilizing their differential sensitivity of orbital coupling to vacancy engineering.

Key words: Nitrogen reduction reaction, Hydrogen evolution reaction, Molybdenum disulfide, Vacancy engineering, Differential orbital-coupling response

Dezhi Wang, Songhua Yang, Yiyi Yangliu, Xufa Peng, Fangyang Liu, Hao Fei, Zhuangzhi Wu. Decoupling competitive reactions by their differential orbital-coupling response to vacancy engineering for efficient electrocatalytic nitrogen reduction[J]. Chinese Journal of Catalysis, 2026, 86: 181-190.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65043-7

https://www.cjcatal.com/EN/Y2026/V86/I7/181

Figures/Tables 5

Fig. 1. (a) HRTEM images of MoS2-100. (b,c) Magnified HRTEM images corresponding to the area framed by the white rectangle in panel (a). (d-f) EDX elemental distribution maps of MoS2-100.

Fig. 2. XRD (a) and Raman patterns (b). (c) EPR intensity of the samples. XPS spectra of Mo 3d (d) and S 2p (e) over the samples. (f) 1T phase and 2H phase concentration of the samples. (g) S/Mo atomic ratio of the samples.

Fig. 3. (a) LSV curves of MoS2-100 in N2- and Ar-saturated 0.1 mol L-1 K2SO4 electrolyte. (b) Properties of MoS2-100. (c) Properties of each sample at different applied potentials. (d) Properties of each sample at ?0.7 V. (e) NH3 yield and corresponding UV-vis spectra after 2 h of electrolysis under different operating conditions. (f) 1H NMR spectra with different feeding gas. (g) NRR performance of MoS2-100 under cyclic alternation between N2- and Ar-saturated electrolytes. (h) Current density-time curves and cycle stability test of MoS2-100 at ?0.7 V.

Fig. 4. (a) Current density as a function of scanning rate for various samples. (b,c) In-situ EIS Bode phase spectra of MoS2-0 and MoS2-100 measured in N2 and Ar atmospheres. (d,e) The potential-dependent in-situ SERS of MoS2-0 and MoS2-100 at different applied potentials. All spectra were normalized by the peak intensity of SO42- for better comparison. (f) The peak intensities of MoS2-100 at different applied potentials. (g) The difference in peak intensities between MoS2-100 and MoS2-0 at different applied potentials.

Fig. 5. (a) The Gibbs free energy diagram of 3S-FGJ along different NRR pathways. (b) Charge density difference of *N2 on 3S-FGJ. Electron accumulation and depletion are represented by red and cyan isosurfaces, respectively. (c) The COHP of the N≡N in adsorbed N2. (d) The relationship between NRR activity and the corresponding ICOHP of Mo-N. (e) Adsorption energy and Eb contrasts between NRR and HER. (f) The relationship between HER activity and the corresponding ICOHP of Mo-H.

References

[1]	B. Lee, L. R. Winter, H. Lee, D. Lim, H. Lim, M. Elimelech, ACS Energy Lett., 2022, 7, 3032-3038.
[2]	B. Wang, T. Li, F. Gong, M. H. D. Othman, R. Xiao, Fuel Process. Technol., 2022, 235, 107380.
[3]	Y. Feng, L. Jiao, X. Zhuang, Y. Wang, J. Yao, Adv. Mater., 2025, 37, 2410909.
[4]	W. Liu, M. Xia, C. Zhao, B. Chong, J. Chen, H. Li, H. Ou, G. Yang, Nat. Commun., 2024, 15, 3524.
[5]	C. Liu, G. Xu, T. Wang, JACS Au, 2023, 3, 3374-3380.
[6]	J. W. Erisman, M. A. Sutton, J. Galloway, Z. Klimont, W. Winiwarter, Nat. Geosci., 2008, 1, 636-639.
[7]	X. Wang, Y. Zhang, H. Si, Q. Zhang, J. Wu, L. Gao, X. Wei, Y. Sun, Q. Liao, Z. Zhang, K. Ammarah, L. Gu, Z. Kang, Y. Zhang, J. Am. Chem. Soc., 2020, 142, 4298-4308.
[8]	D. Gentili, G. Calabrese, E. Lunedei, F. Borgatti, S. A. Mirshokraee, V. Benekou, G. Tseberlidis, A. Mezzi, F. Liscio, A. Candini, G. Ruani, V. Palermo, F. Maccherozzi, M. Acciarri, E. Berretti, C. Santoro, A. Lavacchi, M. Cavallini, Small Methods, 2025, 9, 2401486.
[9]	Q. Jiang, H. Xu, K. S. Hui, Y. Wei, L. Liu, Z. Ye, C. Zha, M. Zheng, J. Lu, K. N. Hui, Adv. Mater., 2025, 37, 2415986.
[10]	W. Yan, J. Xian, S. Zhang, J. Zhang, K. Liu, J.-L. Yang, F. Tao, R. Liu, Q. Liu, P. Yang, Adv. Sci., 2025, 12, 2502834.
[11]	Z. Li, Z. Zhang, J. Lu, Acc. Mater. Res., 2025, 6, 52-63.
[12]	J. Zhou, L. Shen, M. D. Costa, K. A. Persson, S. P. Ong, P. Huck, Y. Lu, X. Ma, Y. Chen, H. Tang, Y.-P. Feng, Sci. Data, 2019, 6, 86.
[13]	G. Zhan, F. Quan, Y. Yao, S. Zhao, X. Liu, H. Gu, Y. Huang, X. Liu, F. Jia, L. Zhang, Appl. Catal. B, 2023, 323, 122186.
[14]	Q. Huang, J. Shen, Y. Lu, R. Ye, S. Gong, J. Phys. Chem. C, 2023, 127, 17406-17414.
[15]	Y. Xiao, M. Zhou, J. Liu, J. Xu, L. Fu, Sci. China Mater., 2019, 62, 759-775.
[16]	R. Liu, H. Fei, J. Wang, T. Guo, F. Liu, Z. Wu, D. Wang, Appl. Catal. B, 2024, 343, 123469.
[17]	Y. Zhang, L. Zhu, H. Xu, Q. Wu, H. Duan, B. Chen, H. He, Molecules, 2023, 28, 2608.
[18]	H. Fei, R. Liu, J. Wang, T. Guo, F. Liu, Z. Wu, D. Wang, Chem. Eng. J., 2023, 476, 146895.
[19]	L. Zhao, S. Liang, L. Zhang, H. Huang, Q.-H. Zhang, W. Ge, S. Wang, T. Tan, L. Huang, Q. An, Small, 2024, 20, 2401537.
[20]	J. Guo, H. Zhao, Z. Yang, L. Wang, A. Wang, J. Zhang, L. Ding, L. Wang, H. Liu, X. Yu, Adv. Funct. Mater., 2024, 34, 2315714.
[21]	Y. Jiang, Y. Zheng, L. Tong, K. Zuo, M. Tu, S. Chen, X. Chen, J. Wu, Q. Chen, X. Li, Y. Chen, Energy Environ. Mater., 2025, 8, e12891.
[22]	H. Fei, R. Liu, J. Wang, T. Guo, Z. Wu, D. Wang, F. Liu, Adv. Funct. Mater., 2023, 33, 2302501.
[23]	X. Guo, E. Song, W. Zhao, S. Xu, W. Zhao, Y. Lei, Y. Fang, J. Liu, F. Huang, Nat. Commun., 2022, 13, 5954.
[24]	D. Wang, X. Zhang, S. Bao, Z. Zhang, H. Fei, Z. Wu, J. Mater. Chem. A, 2017, 5, 2681-2688.
[25]	R. Liu, H. Fei, J. Wang, T. Guo, F. Liu, J. Wang, Z. Wu, D. Wang, Appl. Catal. B, 2023, 337, 122997.
[26]	S. Feng, D. Li, H. Dong, S. Xie, Y. Miao, X. Zhang, B. Gao, P. K. Chu, X. Peng, Appl. Catal. B, 2024, 342, 123451.
[27]	J. Y. Zhang, G. B. Xu, Q. Zhang, X. Li, Y. Yang, L. W. Yang, J. Y. Huang, G. M. Zhou, Adv. Sci., 2022, 9, 2201579.
[28]	S. Z. Andersen, V. Čolić, S. Yang, J. A. Schwalbe, A. C. Nielander, J. M. McEnaney, K. Enemark-Rasmussen, J. G. Baker, A. R. Singh, B. A. Rohr, M. J. Statt, S. J. Blair, S. Mezzavilla, J. Kibsgaard, P. C. K. Vesborg, M. Cargnello, S. F. Bent, T. F. Jaramillo, I. E. L. Stephens, J. K. Nørskov, I. Chorkendorff, Nature, 2019, 570, 504-508.
[29]	D. Chanda, R. Xing, T. Xu, Q. Liu, Y. Luo, S. Liu, R. A. Tufa, T. H. Dolla, T. Montini, X. Sun, Chem. Commun., 2021, 57, 7335-7349.
[30]	P. Li, Z. Jin, Z. Fang, G. Yu, Angew. Chem. Int. Ed., 2020, 59, 22610-22616.
[31]	M. Wang, S. Liu, H. Ji, T. Yang, T. Qian, C. Yan, Nat. Commun., 2021, 12, 3198.
[32]	T. Zhang, Z. Che, Y. Song, R. Yao, J. Li, Y. Sun, G. Liu, Angew. Chem. Int. Ed., 2025, 64, e202514028.
[33]	J. Li, S. Chen, F. Quan, G. Zhan, F. Jia, Z. Ai, L. Zhang, Chem, 2020, 6, 885-901.
[34]	S. Chung, H. Ju, M. Choi, D. Yoon, J. Lee, Angew. Chem. Int. Ed., 2022, 61, e202212676.
[35]	K. Chu, Y. J. Luo, P. Shen, X. C. A. Li, Q. Q. Li, Y. L. Guo, Adv. Energy Mater., 2022, 12, 2103022.
[36]	S. Chung, D. H. Seo, M. Choi, X. Mao, A. Du, K. Ham, S. Giddey, J. Lee, H. Ju, J. Electroanal. Chem., 2021, 896, 115157.
[37]	S. Zhao, X. Lu, L. Wang, J. Gale, R. Amal, Adv. Mater., 2019, 31, 1805367.
[38]	B. Chang, Z. Cao, Y. Ren, C. Chen, L. Cavallo, F. Raziq, S. Zuo, W. Zhou, Y. Han, H. Zhang, ACS Nano, 2024, 18, 288-298.
[39]	X.-H. Chen, X.-L. Li, T. Li, J.-H. Jia, J.-L. Lei, N.-B. Li, H.-Q. Luo, Energy Environ. Sci., 2024, 17, 5091-5101.
[40]	X. Jia, H. Ren, H. Hu, Y.-F. Song, Chem. Eur. J., 2020, 26, 4150-4156.
[41]	T. Zhang, Z. Che, Y. Song, J. Li, Y. Sun, G. Liu, Chin. Chem. Lett., 2025, 36, 111295.
[42]	W. He, J. Zhang, S. Dieckhöfer, S. Varhade, A. C. Brix, A. Lielpetere, S. Seisel, J. R. C. Junqueira, W. Schuhmann, Nat. Commun., 2022, 13, 1129.
[43]	H. Gu, J. Li, X. Niu, J. Lin, L.-W. Chen, Z. Zhang, Z. Shi, Z. Sun, Q. Liu, P. Zhang, W. Yan, Y. Wang, L. Zhang, P. Li, X. Li, D. Wang, P. Yin, W. Chen, ACS Nano, 2023, 17, 21838-21849.
[44]	Y. Kim, J. Ko, M. Shim, J. Park, H.-H. Shin, Z. H. Kim, Y. Jung, H. R. Byon, Chem. Sci., 2024, 15, 2578-2585.
[45]	R. Q. Liu, T. Guo, H. Fei, Z. Z. Wu, D. Z. Wang, F. Y. Liu, Adv. Sci., 2022, 9, 2103583.
[46]	C. Tsai, H. Li, S. Park, J. Park, H. S. Han, J. K. Nørskov, X. Zheng, F. Abild-Pedersen, Nat. Commun., 2017, 8, 15113.
[47]	Y. Ma, T. Yang, H. Zou, W. Zang, Z. Kou, L. Mao, Y. Feng, L. Shen, S. J. Pennycook, L. Duan, X. Li, J. Wang, Adv. Mater., 2020, 32, 2002177.
[48]	Y. X. Lin, S. N. Zhang, Z. H. Xue, J. J. Zhang, H. Su, T. J. Zhao,G. Y. Zhai, X, H, Li, M. Antonietti, J. S. Chen, Nat. Commun., 2019, 10, 4380.
[49]	G. Lin, Q. Ju, X. Guo, W. Zhao, S. Adimi, J. Ye, Q. Bi, J. Wang, M. Yang, F. Huang, Adv. Mater., 2021, 33, 2007509.
[50]	M. Luo, Z. Zhao, Y. Zhang, Y. Sun, Y. Xing, F. Lv, Y. Yang, X. Zhang, S. Hwang, Y. Qin, J.-Y. Ma, F. Lin, D. Su, G. Lu, S. Guo, Nature, 2019, 574, 81-85.
[51]	Z. Zhao, J. Hao, B. Jia, X. Zhang, G. Wu, C. Zhang, L. Li, S. Gao, Y. Ma, Y. Li, P. Lu, J. Energy Chem., 2023, 83, 79-89.
[52]	N. R. Singstock, C. B. Musgrave, J. Am. Chem. Soc., 2022, 144, 12800-12806.
[53]	J. Zhou, X. Chen, M. Guo, W. Hu, B. Huang, D. Yuan, ACS Catal., 2023, 13, 2190-2201.